The present invention relates to coating flexible materials or supports such as sheets of paper or other polymeric material, either woven or non-woven, with a silicone composition. The present invention also relates to the coating of flexible materials or supports with liquid compositions comprising one or more cross-linkable polyorganosiloxanes wherein such polyorganosiloxanes are cross-linkable by an addition reaction, a condensation reaction, a cationic reaction, or a free-radical reaction. The present invention also relates to star branched polyorganosiloxanes (silicone polymers) that reduce misting during the application of the silicone composition (polyorganosiloxane) to the flexible material or support. The flexible support may be paper, cardboard, plastic film, metal film and the like. Some exemplary applications are paper for foodstuffs, adhesive labels, adhesive tapes, seals and the like.
The coating of flexible supports with liquid silicones is typically carried out on coating devices that operate continuously at very high speed. These devices usually comprise coating heads composed of several rolls, including in particular a pressure roll and a coating roll that are continuously fed with a silicone composition that may or may not be cross-linkable, by means of a series of rolls that are placed next to one another. A strip of flexible support of the desired material to be coated is fed at high speed between the pressure roll and the coating roll to be coated on at least one of its surfaces. When it is intended to cross link the silicone coating, apparatus to implement a cross linking reaction are positioned downstream of the coating head. The apparatus that implements cross-linking may be for example an oven or an emitter of radiation, e.g. ultraviolet (UV) radiation or an emitter of a beam of electrons (EB).
High speed coating of flexible supports with silicones has been associated with problems associated with the transfer of the silicone liquid (or fluid) from the coating roll to the flexible support, which moves forward through the coating apparatus. One of the particular problems associated with transfer of the silicone liquid from the coating roll to the flexible support is the appearance of a fog, mist or aerosol in the immediate vicinity of the coating head and particularly close to the points of contact between the coating roll and the flexible support being coated. Typically, the density of this fog, mist or aerosol increases with an increase in the forward speed of the flexible support being coated by the apparatus.
The first effect of this transfer problem is to reduce the amount of silicone liquid actually transferred to the flexible support. A second effect is for the droplets comprising the fog, mist or aerosol to condense onto the newly coated flexible support downstream of the coating rolls creating an orange peel effect. This orange peel effect, or coating non-uniformity, creates problems with coverage, the mechanical properties of the coating, e.g. ruboff, and adhesion resistance.
An additional problem caused by non-uniformity in the coating is related to industrial hygiene and the safety of people operating the coating equipment who are working in the vicinity of the coating equipment.
The present invention provides for a composition comprising the hydrosilylation reaction product of:
a) Compound A
b) and an amount xcex1 of CH2xe2x95x90CHRxe2x80x2CHxe2x95x90CH2 where Rxe2x80x2 is a divalent radical selected from the group consisting of halogens, hydrogen, C1 to C60 divalent hydrocarbon radicals, C1 to C60 divalent polyester radicals, C1 to C60 divalent nitrile radicals, C1 to C60 divalent alkyl halide radicals and C1 to C60 divalent polyether radicals and xcex1 greater than b+d+fxe2x88x92gxe2x88x92hxe2x88x92i where Compound A is the hydrosilylation reaction product of:
c) Mxe2x80x2gMaMHbxe2x88x92gDcDxe2x80x2hDHdxe2x88x92hTeTxe2x80x2iTHfxe2x88x92i and
d) (MjMVikDlDVimTnTVio)pQ)q,
where the subscripts a, b, c, d, e, f, g, h, i, j, k, l, m, n, o, p, are zero or positive and q is non-zero and positive, with k+m+o less than b+d+fxe2x88x92gxe2x88x92hxe2x88x92i , p ranges from 0.4 to 4.0, q ranges from 1 to 200 where the ratio between
Mxe2x80x2gMaMHbxe2x88x92gDcDxe2x80x2hDHdxe2x88x92hTeTxe2x80x2iTHfxe2x88x92i and (MjMVikDlDVimTnTVio)pQ)q 
as defined by (b+d+fxe2x88x92gxe2x88x92hxe2x88x92i)/(((k+m+o)p)q) ranges from 50.0 to 0.01, preferably from 10.0 to 0.10; more preferably from 5.0 to 0.20 and most preferably from 4.0 to 0.25 and all sub-ranges there between; and where the compound:
Mxe2x80x2gMaMHbxe2x88x92gDcDxe2x80x2hDHdxe2x88x92hTeTxe2x80x2iTHfxe2x88x92i 
is the hydrosilylation reaction product of
e) MaMHbDcDHdTeTHf and
f) an amount xcex2 of CH2xe2x95x90CHR1 
where xcex2+1xe2x89xa6b+d+f and b+d+fxe2x88x92gxe2x88x92hxe2x88x92i  greater than 0 with 1.5xe2x89xa6b+d+fxe2x89xa6100; 2xe2x89xa6a+bxe2x89xa612; 0xe2x89xa6c+dxe2x89xa61000; 0xe2x89xa6e+fxe2x89xa610 and R1 is a monovalent radical selected from the group consisting of halogens, hydrogen, C1 to C60 monovalent hydrocarbon radicals, C1 to C60 monovalent polyester radicals,
Dxe2x80x2=(CH2CHR1)R9SiO2/2; and
Txe2x80x2=(CH2CHR1)SiO3/2 
with each R2, R3, R4, R5, R6, R7, R8, R9 and R11 independently selected from the group of C1 to C60 monovalent hydrocarbon radicals where the subscripts a, b, c, d, e, f, g, h, and i are zero or positive subject to the limitations that b+d+fxe2x88x92gxe2x88x92hxe2x88x92i greater than 0.
The present invention further provides for a composition to reduce misting during the coating of flexible supports comprising the hydrosilylation reaction product of:
a) Mxe2x80x2gMaMHbxe2x88x92gDcDxe2x80x2hDHdxe2x88x92hTeTxe2x80x2iTHfxe2x88x92i and
b) (MjMVikDlDVimTnTVio)pQ)q where
the subscripts j, k, l, m, n, o and p are zero or positive subject to the limitation that k+m+o greater than 0, k+m+o less than b+d+fxe2x88x92gxe2x88x92hxe2x88x92i, p ranges from 0.4 to 4.0, q is non-zero and positive subject to the limitation that:
(b+d+fxe2x88x92gxe2x88x92hxe2x88x92i)/(((k+m+o)p)q) ranges from 4.59 to 0.25, where
MVi=RViR5R6SiO1/2;
DVi=RViR10SiO2/2;
TVi=RViSiO3/2;
Q=SiO4/2; where
R10 is independently selected from the group of C1 to C60 monovalent hydrocarbon radicals and each RVi is independently selected from the group of C2 to C60 monovalent alkenyl hydrocarbon radicals.
The star branched siloxane compounds of the present invention are made as the reaction product of:
Compound A+xcex1CH2xe2x95x90CHRxe2x80x2CHxe2x95x90CH2 where Rxe2x80x2 is a divalent radical selected from the group consisting of halogens, hydrogen, a to C60 divalent hydrocarbon radicals, C1 to C60 divalent polyester radicals, C1 to C60 divalent nitrile radicals, C1 to C60 divalent alkyl halide radicals and C1 to C60 divalent polyether radicals and mixtures thereof and xcex1 greater than b+d+fxe2x88x92gxe2x88x92hxe2x88x92i where Compound A is the reaction product of:
Mxe2x80x2gMaMHbxe2x88x92gDcDxe2x80x2hDHdxe2x88x92hTeTxe2x80x2iTHfxe2x88x92i and (MjMVikDlDVimTnTVio)pQ)q,
in the presence of a noble metal hydrosilylation catalyst where the subscripts a, b, c d, e, f, g, h, i, j, k, l, m, n, o, p, are zero or positive and q is non-zero and positive, for mixtures of compounds the average values of each of the subscripts will most likely be non-integral, for specific compounds the subscripts will be integral, with k+m+o less than b+d+fxe2x88x92gxe2x88x92hxe2x88x92i , p ranges from 0.4 to 4.0, preferably 0.5 to 3.0, more preferably 0.5 to 2.5 and most preferably 0.5 to 1.5 and all sub-ranges there between and q ranges from 1 to 200, preferably 1 to 100, more preferably 1 to 75 and most preferably 1 to 50 and all sub-ranges there between where the ratio between the hydride containing precursor and the vinyl containing precursor is defined by the following mathematical relationship between the stoichiometric subscripts of the precursors, (b+d+fxe2x88x92gxe2x88x92hxe2x88x92i)/(((k+m+o)p)q) ranges from 50.0 to 0.01, preferably from 10.0 to 0.10; more preferably from 5.0 to 0.20 and most preferably from 4.0 to 0.25 and all sub-ranges there between and specifically including 3.5 to 0.25; 3.0 to 0.25; 2.5 to 0.25 and 2.0 to 0.25 (where these relationships create a stoichiometric excess of the total hydride available for reaction in the hydride compound, Mxe2x80x2gMaMHbxe2x88x92gDcDxe2x80x2hDHdxe2x88x92hTeTxe2x80x2iTHfxe2x88x92i, to the total vinyl available for reaction in the MQ resin, (MjMVikDlDVimTnTVio)pQ)q); and where the compound:
Mxe2x80x2gMaMHbxe2x88x92gDcDxe2x80x2hDHdxe2x88x92hTeTxe2x80x2iTHfxe2x88x92i,
may be obtained by the following reaction
MaMHbDcDHdTeTHf+xcex2CH2xe2x95x90CHR1xe2x86x92Mxe2x80x2gMaMHbxe2x88x92gDcDxe2x80x2hDHdxe2x88x92hTeTxe2x80x2iTHfxe2x88x92i 
where xcex2+1 xe2x89xa6b+d+f and b+d+fxe2x88x92gxe2x88x92hxe2x88x92i  greater than 0 (these mathematical limitations on the subscripts and the stoichiometric coefficient beta are to insure that the hydride, MaMHbDcDHdTeTHf, is in stoichiometric excess as regards the molar quantity of silicon bonded hydrogen available for reaction, relative to the molar quantity of olefin, CH2xe2x95x90CHR1) with 1.5 xe2x89xa6b+d+fxe2x89xa6100; 2xe2x89xa6a+bxe2x89xa612; 0xe2x89xa6c+dxe2x89xa61000; 0xe2x89xa6e+fxe2x89xa610 and R1 is a monovalent radical selected from the group consisting of halogens, hydrogen, C1 to C60 monovalent hydrocarbon radicals, C1 to C60 monovalent polyester radicals, C1 to C60 monovalent nitrile radicals, C1 to C60 monovalent alkyl halide radicals, C1 to C60 monovalent polyether radicals and mixtures thereof; with
M=R2R3R4SiO1/2;
MH=HR5R6SiO1/2;
MVi=RViR5R6SiO1/2;
D=R7R8SiO2/2;
DH=HR9SiO2/2;
DV=RViR10SiO2/2;
T=R11SiO3/2;
TH=HSiO3/2;
TVi=RViSiO3/2;
Q=SiO4/2;
Mxe2x80x2=(CH2CHR1)R5R6SiO1/2;
Dxe2x80x2=(CH2CHR1)R9SiO2/2; and
Txe2x80x2=(CH2CHR1)SiO3/2 
with each R2, R3, R4, R5, R6, R7, R8, R9, R10, and R11 independently selected from the group of C1 to C60 monovalent hydrocarbon radicals and each RVi independently selected from the group of C2 to C60 monovalent alkenyl hydrocarbon radicals. Methods for making MQ resins, such as (MjMVikDlDVimTnTVio)pQ)q, are described in U.S. Pat. Nos. 5,817,729, 5,399,614 and 2,676,182 herewith and hereby specifically incorporated by reference. The phrase C1 to C60 is a carbon number range ranging from 1 to 60 and includes both aliphatic and aromatic radicals, e.g. styryl, this range also includes the following specific sub-ranges, 15 to 60, 30 to 60, 45 to 60, 1 to 15, 1 to 30, 1 to 45, 10 to 30, 10 to 40, 10 to 50 and all sub-ranges therebetween.
The star branched silicone compounds of the present invention are described as the reaction product of the following two compounds:
Mxe2x80x2gMaMHbxe2x88x92gDcDxe2x80x2hDHdxe2x88x92hTeTxe2x80x2iTHfxe2x88x92i and (MjMVikDlDVimTnTVio)pQ)q, because of the multiplicity of hydrosilylation sites available for reaction on each of the component molecules being reacted and the difficulties of reducing such a stochastic chemical reaction to an analytic description.
The compositions of the present invention may be made by neat reactions or by reactions where the reactants are diluted by solvent. Because of the long chain nature of the substituents in these materials, neat reactions, i.e. reactions conducted in the absence of any non-participating solvent, will tend to produce products that conform to the molecular descriptions herein but possessing a more entangled macro-structure. If less entangled macro-structures of these compounds are desired, the preparative reactions should be conducted in suitable solvent media, e.g. cyclic siloxanes, inert hydrocarbon solvents and the like.
Many types of noble metal catalysts for this hydrosilylation reaction are known and such catalysts may be used for the reaction in the present instance. When optical clarity is required the preferred catalysts are catalysts that are soluble in the reaction mixture. By noble metal, Applicants define Ru, Rh, Pd, Os, Ir, and Pt as noble metals and also include Ni in the definition because of its known hydrogenation activity. Preferably the catalyst is a lo platinum compound and the platinum compound can be selected from those having the formula (PtCl2Olefin) and H(PtCl3Olefin) as described in U.S. Pat. No. 3,159,601, hereby incorporated by reference. The olefin shown in the previous two formulas can be almost any type of olefin but is preferably an alkenylene having from 2 to 8 carbon atoms, a cycloalkenylene have from 5 to 7 carbon atoms or styrene. Specific olefins utilizable in the above formulas are ethylene, propylene, the various isomers of butylene, octylene, cyclopentene, cyclohexene, cycloheptene, and the like.
A further platinum containing material usable in the compositions of the present invention is the cyclopropane complex of platinum chloride described in U.S. Pat. No. 3,159,662 hereby incorporated by reference.
Further the platinum containing material can be a complex formed from chloroplatinic acid with up to 2 moles per gram of platinum of a member selected from the class consisting of alcohols, ethers, aldehydes and mixtures of the above as described in U.S. Pat. No. 3,220,972 hereby incorporated by reference.
The catalyst preferred for use with liquid injection molding compositions are described in U.S. Pat. Nos. 3,715,334; 3,775,452; and 3,814,730 to Karstedt. Additional background concerning the art may be found at J. L. Spier, xe2x80x9cHomogeneous Catalysis of Hydrosilation by Transition Metalsxe2x80x9d, in Advances in Organometallic Chemistry, volume 17, pages 407 through 447, F.G.A. Stone and R. West editors, published by the Academic Press (New York, 1979). Persons skilled in the art can easily determine an effective amount of platinum catalyst. Generally, an effective amount for hydrosilylation ranges from about 0.1 to 50 parts per million of the total organopolysiloxane composition and all sub-ranges there between.